Influence of Azolla on CH4 Emission from Rice Fields

Azolla is an aquatic fern that has been used successfully as a dual crop with wetland rice. Rice fields are a major source of atmospheric CH₄, which is an important greenhouse gas. In this study, field and laboratory experiments showed that growing Azolla as a dual crop could enhance CH₄ emission from rice fields. In pot experimen indications showed that Azolla could mediate CH₄ transport from the floodwater of a rice soil into the atmosphere. It was also found that due to the presence of Azolla, chemical soil properties could be developed, stimulating CH₄ production and decreasing in situ CH₄ removal.     

The Effects of Cultural Practices on Methane Emission from Rice Fields

A field experiment was conducted in a clayey soil to determine the effects of cultural practices on methane (CH₄) emissions from rice fields. The factors evaluated were a) direct seeding on dry vs wet soil, b) age of transplanted seedlings (8 d old and 30 d old), and c) fall vs spring plowing. Methane emissions were measured weekly throughout the rice-growing season using a closed static chamber technique. Transplanted 8-d-old seedlings showed the highest emission of 42.4 g CH₄ m^–2 season^–1, followed by transplanted 30-d-seedlings (40.3 g CH₄ m^–2 season^–1), and direct seeding on wet soil (37.1 g CH₄ m^–2 season^–1). Direct seeding on dry soil registered the least emission of 26.9 g CH₄ m^–2 season^–1. Thus transplanting 30-d-old seedlings, direct seeding on wet soil, and direct seeding on dry soil reduced CH₄ emission by 5%, 13%, and 37%, respectively, when compared with transplanting 8-d-old seedlings. Methane emission under spring plowing was 42.0 g CH₄ m^–2 season^–1 and that under fall plowing was 31.3 g CH₄ m^–2 seasons^–1. The 26% lower emission in the field plowed in spring was caused by degradation of organic matter over the winter.     

Methane steam reforming for synthetic diesel fuel production from steam-hydrogasifier product gases

Steam-methane reforming (SMR) reaction was studied using a tubular reactor packed with NiO/γ-Al₂O₃ catalyst to obtain synthesis gases with H₂/CO ratios optimal for the production of synthetic diesel fuel from steam-hydrogasification of carbonaceous materials. Pure CH₄ and CH₄-CO₂ mixtures were used as reactants in the presence of steam. SMR runs were conducted at various operation parameters. Increasing temperature from 873 to 1,023 K decreased H₂/CO ratio from 20 to 12. H₂/CO ratio decreased from 16 to 12 with pressure decreasing from 12.8 to 1.7 bars. H₂/CO ratio also decreased from about 11 to 7 with steam/CH₄ ratio of feed decreasing from 5 to 2, the lowest limit to avoid severe coking. With pure CH₄ as the feed, H₂/CO ratio of synthesis gas could not be lowered to the optimal range of 4–5 by adjusting the operation parameters; however, the limitation in optimizing the H₂/CO ratio for synthetic diesel fuel production could be removed by introducing CO₂ to CH₄ feed to make CH₄-CO₂ mixtures. This effect can be primarily attributed to the contributions by CO₂ reforming of CH₄ as well as reverse water-gas shift reaction, which led to lower H₂/CO ratio for the synthesis gas. A simulation technique, ASPEN Plus, was applied to verify the consistency between experimental data and simulation results. The model satisfactorily simulated changes of H₂/CO ratio versus the operation parameters as well as the effect of CO₂ addition to CH₄ feed.     

A La2NiO4-Zeolite Membrane Reactor for the CO2 Reforming of Methane to Syngas

The La₂NiO₄-zeolite membrane was prepared by means of in situ hydrothermal synthesis. Techniques such as XRD, SEM-EDX, and BET were used to acquire information as related to the structure, morphology and the pore size distribution of the membrane. At room temperature, we observed a H₂/CH₄ separation factor of 9.2, considerably higher than the Knudsen diffusion value. With the simultaneous separation of CO and H₂ in the membrane reactor, both CO₂ and CH₄ conversions were enhanced in the CH₄/CO₂ reforming reaction.     

Methane production from anaerobic soil amended with rice straw and nitrogen fertilizers

Laboratory experiments were conducted on the effects of rice straw application and N fertilization on methane (CH₄) production from a flooded Louisiana, USA, rice soil incubated under anaerobic conditions. Rice straw application significantly increased CH₄ production; CH₄ production increased in proportion to the application rate. Urea fertilization also enhanced CH₄ production. The maximum production rate was 17% higher, and occurred 1 week earlier, than that of soil samples which did not receive urea, possibly due to the increase in soil pH following urea hydrolysis. The increase in soil pH following urea hydrolysis may have stimulated CH₄-generating bacteria by providing more optimal soil pH conditions or contributed to the drop in redox potential (Eh). The significant decrease in both the production rate and the total amount of CH₄ by application of NH₄NO₃ was associated with increases in soil Eh after addition of this oxidant. Addition of 300 mg. kg^–1 NO ₃ ^- -N increased soil Eh by 220 mV and almost completely inhibited CH₄ production. However, this inhibitory effect was short-termed. Soon after the applied NO ₃ ^- -N was reduced through denitrification, CH₄ production increased. When (NH₄)₂SO₄ was applied, the inhibition of CH₄ production was not associated with an increase in soil Eh which did not change significantly. A direct inhibitory effect of sulphate on methanogenesis might have been more important.     

Effects of rice cultivars on methane fluxes in a paddy soil

CH₄ emission and its relevant processes involved (i.e. CH₄ production, rhizospheric CH₄ oxidation and plant-mediated CH₄ transport) were studied simultaneously to comprehensively understand how rice cultivars (Yanxuan, 72031, and 9516) at growth stages (early and late tillering, panicle initiation, ripening, and harvest stage) affect CH₄ emission in a paddy soil. Over the entire rice-growing season, Yanxuan had the highest CH₄ emission flux with 5.98 g CH₄ m^–2 h^–1 followed by 72031 (4.48 g CH₄ m^–2 h^–1) and 9516 (3.41 g CH₄ m^–2 h^–1). The highest CH₄ production rate of paddy soils planted to Yanxuan was observed with 18.0 g CH₄ kg_{{ (d.w.soil)}} h^–1 followed by the soil planted to 9516 (17.5 g CH₄ kg_{{ (d.w.soil)}} h^–1). For each cultivar, both rhizospheric CH₄ oxidation ability and plant-mediated CH₄ transport efficiency varied widely with a range of 9.81–76.8% and 15.5–80.5% over the duration of crop growth, respectively. Multiple regression analyses showed that CH₄ emission flux was positively related with CH₄ production rate and rice plant-mediated CH₄ transport efficiency, but negatively with rhizospheric CH₄ oxidation (R ²=0.425 for Yanxuan, P<0.01; R ²=0.426 for 72031, P<0.01; R ²=0.564 for 9516, P<0.01). The contribution of rice plants to CH₄ production seems to be more important than to rhizospheric CH₄ oxidation and plant-mediated transport in impact of rice plants on CH₄ emission.     

Carbon Dioxide Reforming of Methane Over Co-precipitated Ni-Ce-ZrO2 Catalysts

An active and relatively stable Ni-Ce-ZrO₂ catalyst has been designed and prepared conveniently by a novel one-step co-precipitation/digestion method. This catalyst exhibited higher stability compared with a catalyst having the same composition but prepared using the conventional impregnation method. It was found that 15% Ni (w/w) co-precipitated with Ce-ZrO₂ making the cubic phase of Ce_0.8Zr_0.2O₂ gave synthesis gas with CH₄ conversion more than 97% at 800 °C and that the activity was maintained for 100 h during the reaction. The higher activity, conversion and stability of these catalysts are mainly related to the nano-crystalline nature of cubic Ce_1-x Zr _x O₂ producing strong interaction with finely dispersed nano-sized NiO _x crystallites.     

Cooperative Activation in the Synthesis of Flavanone Antioxidants Using a Simple and Highly Efficient Magnetically Recoverable Nano-Cu-CoFe2O4 Catalyst

ABSTRACT

Double mixed Cu_0.5Co_0.5Fe₂O₄ ferrite nanoparticles were found as a highly efficient and magnetically separable nanocatalyst for the synthesis of varied flavanone antioxidants. A wide range of flavanone derivatives were prepared with excellent isolated yields within the short reaction times. The catalyst could be separated using a simple magnetic extraction and reused 6 times with no remarkable loss of activity. The high activity of the prepared catalyst was attributed to the cooperative activation of the carbonyl group by both copper and cobalt via a synergistic catalytic effect that facilitates the Micheal addition of the hydroxyl group to the α,β-unsaturated ketone.     

Partial oxidation of CH4 at low pressure over SiO2 prepared from Si

The oxidation of CH₄ with O₂ at low pressure was carried out over SiO₂ prepared from metal Si. The Si showed only total oxidation activity while the Si partly oxidized to SiO₂ showed high selectivities to CH₃OH and HCHO. The results on SiO₂ prepared from Si were compared with those over commercial silicas. The role of SiO₂ in the CH₄ oxidation was discussed.     

Adsorption of binary CO2/CH4 mixtures using carbon nanotubes: Effects of confinement and surface functionalization

Effect of confinement and surface functionalization in carbon nanotubes (CNTs) on the competitive adsorption of a binary CO₂/CH₄ mixture has been investigated by grand canonical Monte Carlo simulations. Adsorption using CNTs with different functionalization arrangements, different diameters, different functionalization degrees, and different functional groups, such as –COOH, –CO, –OH, –CH₃, is investigated. Effects of (a) the pore textural properties, such as pore size and accessible surface area, and (b) the gas–adsorbent interaction, especially the electrostatic interaction, are discussed. From these results, we discuss the impact that variables such as confinement and surface functionalization have on the performance for CO₂ separation.     

Chemical kinetic modelling of the effect of NO on the oxidation of CH4 under fluidized bed combustor conditions

The ignition and burnout of the volatiles in fluidized bed combustor are essential for its performance and emissions. NO_x are known to sensitize the oxidation of hydrocarbons, CO, and H₂. This effect is relevant especially for fluidized bed combustors, which are operated at relatively low temperatures (i.e. about 850 °C). Different reaction mechanisms and modifications to existing mechanisms have been proposed in the literature to account for these low temperature interactions of NO_x and hydrocarbons. In this work, an existing widely used reaction mechanism is adapted and tested for its capability to describe the NO sensitized oxidation of CH₄ under conditions relevant to fluidized bed combustion. NO lowers the ignition temperature to about 300 °C under the conditions investigated. Three different oxidation paths for the oxidation of CH₄ have been identified and discussed. Their relative importance strongly depends on combustion temperature, indicating that the presence of NO_x significantly affects the oxidation of the volatiles in fluidized bed combustion.     

Methane and nitrous oxide emissions from rice paddy soil as influenced by timing of application of hydroquinone and dicyandiamide

A pot trial and a field experiment were conducted to study the effect of timing of application of nitrification inhibitor dicyandiamide (DCD) on N₂O and CH₄ emissions from rice paddy soil. Four treatments including Treatment CK₁, DCD-1 (application of DCD with basal fertilizer), DCD-2 (DCD with tillering fertilizer) and DCD-3 (DCD with panicle initiation fertilizer), were designed and implemented in pot experiment. Total N₂O and CH₄ emissions from DCD-treated soils were decreased profoundly when compared with that from urea alone (P < 0.05). Application of DCD together with basal fertilizer, tillering fertilizer and panicle initiation fertilizer reduced N₂O emission by 8, 30 and 2%, respectively, while those for CH₄ were 21, 8 and 1%. The field experiment with four treatments was carried out subsequently, and a kind of urease inhibitor hydroquinone (HQ) was also incorporated with DCD simultaneously. The combined use of HQ and DCD with basal fertilizer, tillering fertilizer and panicle initiation fertilizer decreased N₂O emissions by 24, 56 and 17%, respectively, while those for CH₄ were 35, 19 and 12%. N₂O emission was effectively reduced by the inhibitor(s) applied with tillering fertilizer before midseason aeration, while CH₄ emission was effectively decreased by the combined use of inhibitor(s) with basal fertilizer before rice transplanting. Furthermore, an increase in rice yield and a reduction of total global warming potential (GWP) of CH₄ and N₂O could be achieved by using inhibitor(s) in rice paddy field.     

Pressure swing adsorption separation of H2S/CO2/CH4 gas mixtures with molecular sieves 4A, 5A,and 13X

Pressure swing adsorption experiments were carried out for the separation of equimolar mixtures of carbon dioxide and methane containing small amounts of hydrogen sulfide, utilizing 4A, 5A, and 13X molecular sieves. High-purity methane of zero or nearly zero hydrogen sulfide concentration was produced in the adsorption stage with 13X and 5A sieves, at high product recovery rates; high-purity carbon dioxide was obtained with the same sieves in the desorption stage. Zeolite 4A was found capable of raising considerably the hydrogen sulfide concentration in the accumulated desorption product (vs. the adsorption feed) at high recovery rates too. Adsorption selectivity values derived from the experimental results for all three gas pairs were in line with some theoretical predictions and experimental data of the literature.     

Activity of different zeolite-supported Ni catalysts for methane reforming with carbon dioxide

The catalytic performance of Ni based on various types of zeolites (zeolite A, zeolite X, zeolite Y, and ZSM-5) prepared by incipient wetness impregnation has been investigated for the catalytic carbon dioxide reforming of methane into synthesis gas at 700 °C, at atmospheric pressure, and at a CH₄/CO₂ ratio of 1. It was found that Ni/zeolite Y showed better catalytic performance than the other types of studied zeolites. In addition, the stability of the Ni/zeolite Y was greatly superior to that of the other catalysts. A weight of Ni loading at 7 wt.% showed the best catalytic activity on each zeolite support; however, the 7% Ni catalysts produced a higher amount of coke than that of two other Ni loadings, 3 and 5%.     

Catalytic syngas production from greenhouse gasses: Performance comparison of Ru-Al2O3 and Rh-CeO2 catalysts

In this work, 3% Ru-Al₂O₃ and 2% Rh-CeO₂ catalysts were synthesized and tested for CH₄-CO₂ reforming activity using either CO₂-rich or CO₂-lean model biogas feed. Low carbon deposition was observed on both catalysts, which negligibly influenced catalytic activity. Catalyst deactivation during temperature programmed reaction was observed only with Ru-Al₂O₃, which was caused by metallic cluster sintering. Both catalysts exhibited good stability during the 70 h exposure to undiluted equimolar CH₄/CO₂ gas stream at 750 °C. By varying residence time in the reactor during CH₄-CO₂ reforming, very similar quantities of H₂ were consumed for water formation. Reverse water-gas shift (RWGS) reaction occurred to a very similar extent either with low or high WHSV values over both catalysts, revealing that product gas mixture contained near RWGS equilibrium composition, confirming the dominance of WGS reaction and showing that shortening the contact time would actually decrease the H₂/CO ratio in the syngas produced by CH₄-CO₂ reforming, as long as RWGS is quasi equilibrated. H₂/CO molar ratio in the produced syngas can be increased either by operating at higher temperatures, or by using a feed stream with CH₄/CO₂ ratio well above 1.     

Analysis of lithium deinsertion/insertion in LiyFePO4 with a simple mathematical model

The onset of experimental galvanostatic charge/discharge data of Li_yFePO₄ at low current density and at room temperature is analyzed using a single-particle mathematical model. The model contains only two adjustable parameters, namely one related to solid-state diffusion in the active particle and another one related to the surface resistance of the particle. The analysis reveals that these two parameters depend on the current density in a similar manner, meaning that there exists a correlation between them. An immediate consequence is that the onset of the experimental charge/discharge curves is properly modeled with the particle radius as a unique parameter depending on the current density. Hypotheses are made to shed light on this unusual dependence.     

Simultaneous Production of Syngas and Ethylene from Methane by Combining its Catalytic Oxidative Coupling over Mn/Na2WO4/SiO2 with Gas Phase Partial Oxidation

A new route of methane utilization is presented, in which methane is converted to H₂, CO and C₂H₄ simultaneously with equal mole ratio, in order that the produced mixture could be used in the synthesis of propanal via hydroformylation. Kinetically controlled free radical gas phase methane oxidation was combined with its catalytic oxidative coupling over Mn/Na₂WO₄/SiO₂ to concomitantly acquire ethylene and syngas with close concentration. Under the optimal reaction condition, a mole ratio of CO:H₂:C₂H₄=1.0:1:0.9 was obtained with a yield of 11.6% and a selectivity of 68% to the target products based on C, while the selectivity to CO₂ is as low as 18.1%.     

Nitrous oxide and methane emissions from soil–plant systems

The closed chamber method was used to measure the N₂O and CH₄ emissions from rice, maize, soybean and spring wheat fields in Northeast China. Rice field almost did not emit or deposit N₂O in total during flooding period, whereas N₂O was substantially emitted during non-flooding period. The annual emission amount of N₂O was 1.70 kg N₂O ha^-1, but that in flooding period was only 0.04 kg N₂O ha^-1. Daily average and seasonal total CH₄ emission in rice field were 0.07 and 7.40 g CH₄m^-2, respectively. A trade-off between N₂O and CH₄ emissions from rice field was found. The growth of Azolla in rice field greatly stimulated both N₂O and CH₄ emissions. Total N₂O emissions (270 days) from maize and soybean fields were 7.10 and 3.12 kg N₂O ha^-1, respectively. The sink function of the uplands monitored as the atmospheric CH₄ was not significant. This revised version was published online in August 2006 with corrections to the Cover Date.     

Using a Crop/Soil Simulation Model and GIS Techniques to Assess Methane Emissions from Rice Fields in Asia. II. Model Validation and Sensitivity Analysis

The MERES (Methane Emissions from Rice EcoSystems) simulation model was tested using experimental data from IRRI and Maligaya in the Philippines and from Hangzhou in China. There was good agreement between simulated and observed values of total aboveground biomass, root weight, grain yield, and seasonal methane (CH₄) emissions. The importance of the contribution of the rice crop to CH₄ emissions was highlighted. Rhizodeposition (root exudation and root death) was predicted to contribute about 380 kg C ha^–1 of methanogenic substrate over the season, representing 37% of the total methanogenic substrate from all sources when no organic amendments were added. A further 225 kg C ha^–1 (22%) was predicted to come from previous crop residues, giving a total of around 60% originating from the rice crop, with the remaining 41% coming from the humic fraction of the soil organic matter (SOM). Sensitivity analysis suggested that the parameter representing transmissivity to gaseous transfer per unit root length (_r) was important in determining seasonal CH₄ emissions. As this transmissivity increased, more O₂ was able to diffuse to the rhizosphere, so that CH₄ production by methanogens was reduced and more CH₄ was oxidized by methanotrophs. These effects outweighed the opposing influence of increased rate of transport of CH₄ through the plant, so that the overall effect was to reduce the amount of CH₄ emitted over the season. Varying the root-shoot ratio of the crop was predicted to have little effect on seasonal emissions, the increased rates of rhizodeposition being counteracted by the increased rates of O₂ diffusion to the rhizosphere. Increasing the length of a midseason drainage period reduced CH₄ emissions significantly, but periods longer than 6–7 d also decreased rice yields. Organic amendments with low C/N were predicted to be more beneficial, both in terms of enhancing crop yields and reducing CH₄ emissions, even when the same amount of C was applied. This was due to higher rates of immobilization of C into microbial biomass, removing it temporarily as a methanogenic substrate.